Bodying of drying oils



" April 21, 1943. J. D. JEMNS 2,311,915

sonnue OF DRYING OILS Filed April 5, 1940 COOLER Patented Apr. 27, 19432,317,915 BODYING F DRYINGOILS John D. Jenkins, Forest Hills, Pa.,asslgnor to Pittsburgh Plate Glass Company, Allegheny County, Pa., acorporation of Pennsylvania Application April 5, 1940, Serial No.327,972

lClaims. ('01. 260407) The present invention relates to a process ofheat-treating drying oils, such as are employed in the formulation ofpaints and varnishes and the like, and it has particular relation to theprocess of heat-treating such oils for purposes of increasing viscosity,and improving the rate of drying.

One object of the invention is to provide a drying oil which has asubstantially faster drying rate than oils bodied by conventionalmethods.

A second object of the invention is to provide a process of bodyingdrying oils'which admits of removal and saving of free acids containedin the oil.

A third object of the invention is to provide a process of bodyingdrying oils by application of which the oil can be easily and quicklybodied to substantially any desired condition with a minimum ofapparatus and expense.

A fourth object of the invention is' to provide a process of bodyingoils which admits of bodying raw oils without break formation.

These and other objects of the invention will be apparent fromconsideration of the following specification and claims.

In the paint and varnish industry, oils of the nature of linseed oil,soy-bean oil, tung on and the like are employed as film-formingconstituents. Before these oils are added to the paint or varnishcomposition they are often subjected to a process of heat-treatmenttermed bodying, which results in a substantial increase in the body orviscosity of the oil and also results in a product which dries morereadily than the unbodied oil. The bodying process has heretoforeinvolved the heating of the oil in a suitablekettle to a, temperature ofseveral hundred degrees F.

for a period of several'hours. Such process is ity of the product is notalways as great as migh be desired. Furthermore, theoils contained, orproduced during the bodying operation, consid erable amounts of freefatty acids which were within themselves ,valuable for many purposes,such as the formation of artificlal'resins, plasticizers and otherpurposes, but under usual operating conditions,were allowed to waste. g

7 Also, by such process it is practically impossible to body raw oilsbecause of separation of asludge termed breakFwhere the oil reachesatemperature of about 400 or 500 F. V 1

In accordance with the present invention a drying oil ofthe type oflinseedoil, soy-bean oil,

or the like eitherin the raw or the refined state is subjectedto whatmight be termed a continuous bodying operation. involving the continuousfeed of astream of. the, oil into a poolof'oil of appropriate size in abodying kettle and simul-, taneously withdrawing correspondingamounts'of I s the bodied oils: As a fuIther feature the oil in thebodying kettle is continuously blown with an inert gas, such as carbondioxide or flue gas, ,or

nitrogen in such manner that a proportion of the free fatty. acidscontained in the oil are blownout and are recovered by condensation or.by other suitable treatment. 7

For a better understanding of theinvention reference maynow be had tothe accompanying drawing in which the single figure is a diagrarnma'tic'view of an appropriate e nbodimentv of apa paratus suitable foruse in-the practice off the i V invention. 7

typically a batch operation and necessitates that.

each batch of oil b'e'carried through a particular cycle of heating andsubsequent cooling. The

operation is comparatively slow'and' substantial amounts of apparatusare required. in the bodyfrom batch to batch and as a result theuniform- In .the drawing like numerals refer to like parts throughout.The apparatus, may include as a bodying kettle or container l0 formedofany v sultablemetal. This container'is provided with means pp yingheatthereto, for example;

it may be partially or completely enclosed or surrounded bytheelectrical heating'coils-l l .and a ,lagging (not shown) forconserving-heat. Glyc- 7 I 'eride oilsfeither raw or partially; orcompletely refined are; supplied as feed oilto thepcontainer 10 throughga conduit '12, whichgas ,shownin the drawing is'so formed at itsoutlet-extremity as to provide a diagonally downwardly-directed; lip

13 from which the oil continuously runs'as a solid; 1 quiescent stream;that flowsix'itothamainlbody.

. of 011 in the container Hlf vitha minimum "or tu' spl'ashing orturbulence. The container.-is ,'-also,l

' upwardly abouttubes33.

provided with power-driven agitator involving a shaft H having propellorblades i6, which are submerged in the oil.

The kettle or container I is formed with a slightly conical bottom H,which at its apex discharges into an outlet conduit 19 having a controlvalve 2|. In order accurately to control the level and therefore thequantity of oil in the container, it may be provided with a constantlevel overflow pipe, including a vertical portion 22, which may be openat its upper end and at as to insure that the oil flowing oil will havevbeen aflorded a substantial period of time for heat treatment inthe'kettle.

As previously stated, substantial amounts of free acids exist in or areliberated in the drying oil as a result of the heat treatment. In orderto prevent the ratio of these acids from becoming excessive it isdesirable to blanket or to blow the oil with an inert gas, such ascarbon dioxide or the like. This is readily accomplished by conductingthe gas through a conduit 28 and discharging it adjacent to the bottomof the container. The inert gases escaping upwardly through the oil aredischargedthrough a drum 21, at the top of the container and passingoutwardly through conduit 28 to a condenser apparatus comprising ashell'29 of conventional design, involving drum sections and 32 at the top andbottom thereof respectively, and intermediate or connecting tubes 33'through which the vapors and the condensed oil flow downwardly.

The tubes may be cooled by any desired me-.

dium, but preferably the inert gas for the blowingoperation is used as acooling medium and is thereby. preheated before introduction into thekettle. For this purpose the conduit 26' is connected at its upper end36 to the shell 29 below drum'section 3| and receivesgas which isintro-,

duced by conduit 3! having an inlet to shell 23 above drum .32 and whichis heated in its passage The cooled carbon dioxide from the drum 32 isdischargedthrough outlet conduit 38 and may be dried and otherwisetreated preparatory to recycling to the apparatus. It may also bedischarged to the atmosphere or employed for other purposes, if sodesired. The free fatty acids con-' densed from the carbon dioxide inthe tubes 33 are collected in the drum 32 and are discharged to storagethrough the'conduit 39.

Apparatus for cooling the bodied oil discharge from the container in andfor preheating the oil a for inlet to the container through conduit I2is indicated at ll. This apparatus includes a water cooler and'a heatexchange unit 43 intercom,

nected attheir'tops by :a conduit 44, whichin tumis-connected to theoutlet conduit I! for the bodied oil. Valves and" upon: opposite sidesof thelconduit i9 admit of selectively flowing the h'ot'but bodied oileither to the cooler |2or heat exchanger 43-or admits of dividing. theflow of oil to the two units inany desired manner. The

cooler and the heat :exchange unit are ofsub- 'stantially identicalconstructionv and include shells 48 having upper drums 49 andlowerdrurns- II, which are interconnected by tubes 52 in con-- ventionalmanner. The space about the tubes in the cooler 42 is filled withcooling medium, such as water, fed thereto through the conduit 53 anddischarged at the top of the unit through conduit 54.

The heat exchanger 43 is employed to preheat the feed oil to appropriatetemperature, e. g. about 400 to 500 F., which is accomplished by feedingthe oil through conduit 59 to the lower portion of the space about thetubes 52, and drawing it off at the top of the same space through outletEl, which constitutes a continuation of the feed conduit [2. The cooledor partially cooled oil is received in the drums 5| and is dischargedinto the outlet conduit 6 l, which interconnects the drums. Conduits 62and 63, connected to the conduits 6|, lead to a conduit 84 through whichthe bodied oil is discharged to storage.

It is'to be noted that by-pass conduits 66 and B1 are connected toconduit 6! intermediate of the unions or connections to the conduits 62and 63. These by-pass conduits at their upper extremities are Joined tothe conduit 44 upon opposite sides of the valves 46 and 41. Valves 68and 69 are provided in the by-pass conduits and also valves H and 12 aredisposed in the conduit 6| respectively between the by-pass conduits,the cooler 32 and the heat exchanger 43. A valve 13 is further disposedin conduit 6i between the two by-pass conduits. Finally valves 14 and 15are disposed inthe conduits 62 and 63. It will be apparent that byappropriate manipulation of these various valves it is possible todischarge the whole of the bodied oii'either into the heat exchanger orthe cooler, or the oil may be divided in any desired manner.Furthermore, the oil may be discharged from the heat exchanger and thenpassed through the cooler or vice versa,

depending upon operating conditions which it is desired to-obtain. Itwill be apparent also that.

.if desired, the oil may be by-pas sed through con- ,oil is allowed tostay in the bodying kettle for the requisite length of timerto obtain asatisfactory degree of bodying. This willdepend upon the temperature ofthe kettle and the nature of the oil itself. However, in general thetemperature probably, will be around 600 F. The average time in thekettle will vary with'the degree of of bodying required and probablywill be of the order of 1 to 10 hours. Oil introduced into the pool inkettle I0 is brought substantially instantaneously t'o bodyingtemperature.

The oil maybe drawn off, as it is bodied, through the discharge conduitvi 8 by merely opening the valve 2| to the requisite degree, or ifpreferred-the valve 2l may be closed and the oil allowed to discharge atthe desired rate through throughconduit l9:to the water cooler 42 or the7 heat exchanger 43 where it iscooled to the.de-

sired degree before 'passing to storage.

The feed of carbon dioxide or other inert gas into the kettle willdepend upon theacidity desired in the final product. A certain degree ofacidity is perhaps desirable and maybe obtained by increasing ordecreasing the flow of inert gas, in order to blow away any excesses ofthe acids.

The following represent typical operating conditions for the bodying oflinseed oil.

TABLE I.Lightly bodied linseed oils NOTE 1.-50 a by weight in acetone.Nora g-GS F., 65% relative humidity. Samples aged 20 hours beloretesting.

The oils marked in the table as Refined were subjected to alkalirefinement prior to the bodying operation. The oils marked "Raw weretypical linseed oils without the alkali refinement treatment. Theproperties of these bodied oils may be compared with those of a typicalalkali refined oil which was bodied by a conventional 7 These propertiesare tabulated batch process.

It is to be observed that the alkalirefined oil. when continuouslybodied by the process herein disclosed, possesses. a substantially morerapid rate of drying than the corresponding oil bodied by conventionalmethods. For example, it ,will

be observed that infthe case of the conventional product the dryingrateswere respectively 9.4 and hours dependent upon the drier which wasadded thereto. In contradistinction, the alkali refined oil, when bodiedby the present process,

dried in periods of 5.7, 3.8, 4.8 and 2.9 hours, dependent upon thecatalyst and the degree of bodying. The raw oil dried in periods of 6.7,4.6, 5.3 and 2.9 hours, likewise dependent upon the catalyst and thedegree orbodying to which.

it was subjected.

The oil when continuously bodied in accord ance with the presentinvention-is. subjected to substantially different conditions than existin a conventional batch process. In a batch operation the oil isrelatively slowly brought to bodying conditions and all of the oil issubjected'simultaneously to the same conditions and there isa tendencyfor all portions of it to go through the same reactions. The reactionsof courseinclude various polymerizations ,in which monomeric glyceridesare added together to forrndimers and subsequently dlmersareadded-together or' V for equilibrium to be reached, a veryhighpercentage of the oil in the polymerization zone is Feed oil 7 RefinedRaw Temperature of operation, F 603 608 Feed rate, gall/hr 10 10 Av.treatment time, hrs 2 2 CO1, wt. percent of feed oil 9. 7 6 F. A.distillate, percent of feed oil 1.3 Ratio wt. Col/wt. distillate 7. 5

Properties of produda Vis., cup at 25 0., sec '11 8 Color, Gardner 2. 5Greenish Acid number..-.. 6. 7 8. Iodine value 134 136 Refractive indexL 1. 4859 1.4852 griitinsohitem (N (rite 3.2).. I 4.0 Below 0 r g t me,rs. o

.3% Pb, 03% Mn 5. 7 6. 7 .0o% 00 3. s 4. 0

TABLE II.-Heam'ly bodied linseed oils Feed oil Refined Raw Temp. 0!operation, F 608 608 Feed rate, gaL/hr 2. 5 2. Ave. treatment time, hrs8 7. 3 00; wt. percent of feed oil 38 33 F. A. distillate. peroentoifeed 0 8 l0 Ratio Co /distillate 4.8 3.3

Properties ofproducta Vis. M" cup'at 25 0., sec 210 195 Color, Gardner 45 Acid number 12.7 13. 9 Iodine value 116 Refractive index l. 4927 l.4924 Crit. sol. temp, 0 0. (Note 1 39.6 37.7 Drying time, hrs. (Note 2):

3% Pb, .03% Mn 4. 8 5. 3

06% Co 2. 9 2. o

" formation is passed almost instantly and break in the condition of arelatively high polymer. The feed oil, which at any particular time ispresent in the reaction mass in only a relatively small amount, isailorded an especially good opportunity for contact and reaction oraddition to the higher-polymers and there is but little opportunity forcontact of monomer with monomer. Therefore, it isto be expected thatrelatively small amounts of the dimer will be present in the bodied oiland proportionally there will be a relatively large amount of highly.polymerized material present.

applicants product. a l V Applicants process is'of particular value inthe bodylng or raw. or unrefined drying oils, such as I linseed; soyabean, and the like, because'raw oils, when heated to a temperature ofabout 400 or 500 F. undergo break formation. 'A slime is produced thatfor most practical purposes can not be removed. However, in applicantsprocess,

ii oil below "break" temperature is run into the I l pool ofbodying oil,the temperatureoi' "break" does not separate. The hotoil can then bebodied? A slightly bodied raw oil can be taken oil from the apparatusand then batch'bo'died,

if so desired. 1 v V The sudden heating seemsto result in fixation ofthe "break in the oil so that it does not separate during bodying.Presumably 'the'bodied raw oil still contains the break-formingconstituents.

It is to be understood that the intermittent or pulsating feed of raw orrefined oil into the body- I ing kettle and corresponding withdrawals o!bodied oil is contemplated. Likewise, it may sometimes be desirable torun oil, raw or refined, into a kettle which initially contains'only asmall discharge is effected.

The forms of. the invention scop ortne'apn claims.

This perhaps tends to explainthe relatively high vrate of dryingofsuificiently bodied,

herein-disclosed and described are to be understood merely.;as,exemplary and it will be'apparent' that numerous" .rnodlflcations may bemade therein without de parture from thespirit of; the invention or thel What I claim is: a v

1. A process of bodying without "break formation raw drying oils from aclass consisting of linseed and soy-bean oil, but containing breakformconstituents, which process comprises continuously feeding unbodled rawdrying oil into a pool of oil heated to the bodying temperature,substantially instantaneously admixing the feed oil with the oil of the.pool and correspondingly withdrawing the bodied oil,-the rate of feedand withdrawal of the: oil being so adjusted that the desired degree ofbodying is obtained while the oil is in the heated pool, and bubblinginto the oil in the pool an inert gaseous medium, in order to-removefree acids therefrom. *2. A process of bodying without break" formationraw drying oils from a class consisting of linseed and soy-bean, oil,which comprises bringingthe oil from a temperature below that of breakformation to bodying temperature substantially instantaneously and thenmaintaining the oil at bodying temperature until a desired degree ofbodying has been reached.

3. A process of bodying without break" formation raw, drying, glycerideoils from a class consisting of linseed and soy-bean oil and containing"break-forming constituents, which process comprises feeding the oil asa streaminto a pool of oil heated to 'bodying'temperature whereby tobring the feed oil substantially instantaneously to bodying temperature,and drawing'off bodied v oil as raw oil is fed in.

whereby to heat the feed oil substantially instantaneously to thebodying temperature, and correspondingly drawing oil oil from the pool,the pool being of such size that the oil is incompletely bodied while itis therein, and subsequently completing the bodying operation by furtherheating the oil in a batch operation.

5. A process of bodying without break formation drying oil from a classconsisting of linseed and soy-bean oil and containing break-formingconstituents, which process comprises running unbodied oil as a freefalling stream into a pool of the oil heated to the bodying temperature,the temperature being maintained during the addition, then drawing ofifthe oil after it has been bodied.

6. A process of bodying without "break formation raw drying oils from aclass consisting of linseed and soy-bean oil, but containingbreakforming constituents, which process comprises flowing the feed oilas a continuous stream into an agitated pool of oil at an elevatedtemperature under such conditions that the oil becomes substantiallyinstantaneously heated to the temperature of the pool, said temperaturebeing sumciently high to obviate ,break-forming tendencies in the oil,then subsequently bodying the oil.

7. A process of bodying a refined, drying, glyceride oil from a classconsisting of linseed and soy-bean oil to obtain a product of dryingproperties superior to those of the same oil when batch bodied, whichprocess comprises feeding the oil as a stream intoa pool of the oilheated to the bodying temperature" and substantially instantaneouslymixing the feed oil with the heated oil in the pool, maintaining the oilin the pool until it is substantially bodied,a nd withdrawing bodied oilat approximately the rate at which it is fed in. V

. JOHN D. JENKINS.

